CN110627841A - Iron complex containing m-carborane triazole ligand and preparation and application thereof - Google Patents

Iron complex containing m-carborane triazole ligand and preparation and application thereof Download PDF

Info

Publication number
CN110627841A
CN110627841A CN201910928582.2A CN201910928582A CN110627841A CN 110627841 A CN110627841 A CN 110627841A CN 201910928582 A CN201910928582 A CN 201910928582A CN 110627841 A CN110627841 A CN 110627841A
Authority
CN
China
Prior art keywords
carborane
iron complex
room temperature
meta
triazole ligand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910928582.2A
Other languages
Chinese (zh)
Other versions
CN110627841B (en
Inventor
姚子健
乔新超
朱经纬
林楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Technology
Original Assignee
Shanghai Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN201910928582.2A priority Critical patent/CN110627841B/en
Publication of CN110627841A publication Critical patent/CN110627841A/en
Application granted granted Critical
Publication of CN110627841B publication Critical patent/CN110627841B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to an iron complex containing a meta-carborane triazole ligand, and preparation and application thereof, wherein the preparation method of the iron complex comprises the following steps: 1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature; 2) adding 3-bromopropyne, reacting at room temperature for 2-4h, draining the solvent after the reaction is finished, and recrystallizing to obtain 1, 3-dipropargyl m-carborane; 3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst in an organic solvent, and reacting at room temperature for 3-6 h; 4) adding FeCl2Reacting at room temperature for 5-8h, and separating; the iron complex is used for catalyzing and oxidizing aromatic hydrocarbon to synthesize aromatic alcohol. Compared with the prior art, the invention adopts a one-pot method to obtain the iron complex containing the meta-carborane triazole ligand, the synthesis process is simple and green, and the iron complex can efficiently catalyze and oxidize aromatic hydrocarbon to prepare the aromatic alcohol compound under the condition that hydrogen peroxide is used as an oxidant.

Description

Iron complex containing m-carborane triazole ligand and preparation and application thereof
Technical Field
The invention belongs to the technical field of synthetic chemistry, and relates to an iron complex containing a meta-carborane triazole ligand, and preparation and application thereof.
Background
Since the synthesis of carboranes in the sixties of the twentieth century, compounds with stable chemical properties have attracted considerable interest and have become an active area in modern chemical research. Due to its special physicochemical properties, carborane derivatives are widely used in molecular recognition, liquid crystal materials, nonlinear optical materials and synthesis of polymer materials. The carborane-based metal complexes are also widely applied to organic synthesis as catalysts. In contrast, the metal complexes with ortho-carborane as a building block have been studied most extensively, while the complexes with meta-carborane structure are relatively rare and lack of understanding of their properties. Therefore, it is necessary to explore metalorganic compounds based on meta-carborane ligands and their use in organic synthesis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an iron complex containing a m-carborane triazole ligand, and preparation and application thereof. The preparation method of the iron complex is simple and green, and the iron complex can be obtained in high yield through one-pot reaction. The iron complex can efficiently catalyze and oxidize aromatic hydrocarbons to synthesize alcohol compounds, and has the advantages of mild reaction conditions, good universality, high catalysis efficiency, few byproducts, lower cost, easy product separation and no generation of a large amount of waste residues. And the iron complex is used as a catalyst, has high stability and is insensitive to air and water.
The purpose of the invention can be realized by the following technical scheme:
an iron complex containing a meta carborane triazole ligand, the iron complex having the formula:
wherein R is H, OMe, NO2One of Cl or Br, "·" is a boron hydrogen bond.
A method for preparing an iron complex containing a meta carborane triazole ligand, the method comprising the steps of:
1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature;
2) adding 3-bromopropyne, reacting at room temperature for 2-4h, draining the solvent after the reaction is finished, and recrystallizing to obtain 1, 3-dipropargyl m-carborane;
3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst in an organic solvent, and reacting at room temperature for 3-6 h;
4) adding FeCl2Reacting for 5-8h at room temperature, and separating to obtain the iron complex.
Wherein, the reaction processes of the step 1) and the step 2) are as follows:
the reaction process of the step 3) and the step 4) is as follows:
further, in the step 1), the n-BuLi solution is n-hexane solution of n-BuLi, and the m-carborane solution is m-carborane (m-C)2B10H12) B ofAnd (3) ether solution.
Further, the step 1) is specifically as follows:
1-1) dropwise adding the n-BuLi solution into the meta-carborane solution at the temperature of between-5 and 5 ℃, and then continuously stirring for 25 to 35 min;
1-2) heating to room temperature, and continuing to react for 30-60 min.
Further, in the step 2), after the reaction is finished, the solvent is drained, and the 1, 3-dipropargyl m-carborane is obtained by n-hexane recrystallization.
Further, in the step 3), the catalyst is CuI, and the organic solvent is Tetrahydrofuran (THF).
Further, in step 4), the separation process is as follows: after the reaction is finished, standing and filtering, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product. The eluent used for column chromatography separation is a mixed solvent consisting of dichloromethane and ethyl acetate with the volume ratio of (3-5): 1.
Further, the catalyst, 1, 3-dipropargyl meta-carborane, aryl azide and FeCl2The molar ratio of (1) to (1.2-1.5) is 0.05:1.0 to 1.
An application of an iron complex containing a meta-carborane triazole ligand is disclosed, and the iron complex is used for catalyzing and oxidizing aromatic hydrocarbon to synthesize aromatic alcohol.
Further, in the catalytic oxidation process, hydrogen peroxide is used as an oxidant; the aromatic hydrocarbon comprises one or more of ethylbenzene, 2-methyl ethylbenzene, 3-methyl ethylbenzene, 4-methoxy ethylbenzene, 4-chloro ethylbenzene, 4-nitro ethylbenzene, n-propylbenzene, n-butylbenzene, 2-ethyl naphthalene or isopropylbenzene.
The specific application method is as follows: dissolving arene in methanol under the condition of taking the prepared iron complex as a catalyst, and using hydrogen peroxide H2O2(the mass fraction is 30%) as an oxidant, reacting at room temperature for 6-8 hours, and after the reaction is finished, concentrating the reaction solution and separating by silica gel column chromatography to obtain the corresponding aromatic alcohol. Wherein, the iron complex, the aromatic hydrocarbon and H2O2The molar ratio of (0.02-0.05) to (1.0-1.5-2.0).
The invention is provided with1, 3-dipropargyl meta-carborane is used as a raw material and reacts with aryl azide under the catalysis of CuI to generate a meta-carborane triazole ligand, and FeCl is added2The iron complex containing the meta-carborane triazole ligand is obtained by adding a reaction system and a one-pot method, and the synthesis process is simple and green and has excellent selectivity and higher yield. The iron complex prepared by the invention can efficiently catalyze and oxidize aromatic hydrocarbon to prepare aromatic alcohol compounds under the condition of taking hydrogen peroxide as an oxidant.
Compared with the prior art, the invention has the following characteristics:
1) the preparation method of the iron complex containing the m-carborane triazole ligand is simple, the iron complex can be prepared in high yield through one-pot reaction and can stably exist in the air;
2) the iron complex can efficiently catalyze and oxidize aromatic hydrocarbon to synthesize aromatic alcohol, has good selectivity and mild reaction conditions, and uses simple and clean hydrogen peroxide H2O2The synthesis of aromatic alcohol can be realized by using the oxidant.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
synthesis of 1, 3-dipropargyl meta-carborane:
n-BuLi (22.0mmol) in n-hexane was added dropwise to the m-C m-carborane at 0 deg.C2B10H12(10.0mmol) of ethyl ether solution, continuously stirring for 30 minutes after the dropwise addition is finished, slowly raising the temperature to room temperature, continuously reacting for 30 minutes, adding 3-bromopropyne (21.0mmol), continuously reacting for 3 hours at room temperature, draining the solvent after the reaction is finished, and recrystallizing the product by n-hexane to obtain the 1, 3-dipropargyl m-carborane C8B10H16(yield 85%).1H NMR(400MHz,CDCl325 ℃ C.). delta.3.55 (s, 2H.), 2.63(s, 4H.) theoretical value of elemental analysis C8B10H16: c43.61, H7.32; experimental values: c43.55, H7.30.
Example 2:
synthesis of iron complex 1 containing m-carborane triazole ligand:
CuI (0.05mmol), 1, 3-dipropargylpropyl m-carborane (1.0mmol) and azidobenzene (1.2mmol) were dissolved in THF at room temperature, reacted at that temperature for 3 hours, and then FeCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 5 hours. After the reaction, the reaction mixture was left to stand and filtered, and the solvent was dried under reduced pressure, and the obtained crude product was subjected to column chromatography (dichloromethane/ethyl acetate: 5:1) to obtain brown iron complex 1 as an objective product (yield 73%).1H NMR(400MHz,CDCl325 ℃ C.: δ 8.35(s,2H),7.80(d, J ═ 7.0Hz,4H),7.63(d, J ═ 7.2Hz,2H),7.42(t, J ═ 6.8Hz,4H),3.20(s,4H), elemental analysis theoretical value C20B10H26Cl2N6Fe: c41.04, H4.48, N14.36; experimental values: c41.08, H4.45, N14.38.
Example 3:
synthesis of iron complex 2 containing m-carborane triazole ligand:
CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and 4-methoxyazidobenzene (1.5mmol) were dissolved in THF at room temperature, reacted at this temperature for 6 hours, and then FeCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 6 hours. After the reaction is finished, standing and filtering are carried out, the solvent is drained under reduced pressure, and the obtained crude product is subjected to column chromatography separation (dichloromethane/ethyl acetate ═ 3:1) to obtain brown target product iron complex 2 (yield is 78%).1H NMR(400MHz,CDCl3,25℃):δ＝8.30(s,2H),7.76(d,J＝7.2Hz,4H),7.59(d, J ═ 7.2Hz,4H),3.45(s,6H),3.15(s,4H)22B10H30Cl2N6FeO2: c40.94, H4.69, N13.02; experimental values: c40.99, H4.67, N13.05.
Example 4:
synthesis of iron complex 3 containing m-carborane triazole ligand:
CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and 4-nitroazidobenzene (1.3mmol) were dissolved in THF at room temperature, reacted at that temperature for 6 hours, and then FeCl was added2(1.0mmol) was added to the reaction system and reacted for another 8 hours. After the reaction, the reaction mixture was left to stand and filtered, and the solvent was dried under reduced pressure, and the obtained crude product was subjected to column chromatography (dichloromethane/ethyl acetate: 5:1) to obtain brown iron complex 3 as an objective product (yield 85%).1H NMR(400MHz,CDCl325 ℃ C.: δ 8.29(s,2H),7.88(d, J ═ 7.2Hz,4H),7.71(d, J ═ 7.2Hz,4H),3.26(s,4H), elemental analysis theoretical value C20B10H24Cl2N8FeO4: c35.57, H3.58, N16.59; experimental values: c35.59, H3.65, N16.55.
Example 5:
synthesis of iron complex 4 containing m-carborane triazole ligand:
CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and 4-chloroazidobenzene (1.2mmol) were dissolved in THF at room temperature, reacted at that temperature for 3 hours, and then FeCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 6 hours. After the reaction, the reaction mixture was left to stand and filtered, and the solvent was dried under reduced pressure, and the obtained crude product was subjected to column chromatography (dichloromethane/ethyl acetate ═ 3:1) to obtain brown iron complex 4 as an objective product (yield 77%).1H NMR(400MHz,CDCl3,25℃):δ＝8.36(s,2H),7.89(d, J ═ 7.2Hz,4H),7.77(d, J ═ 7.2Hz,4H),3.21(s,4H)20B10H25Cl3N6Fe: c38.76, H4.07, N13.56; experimental values: c38.78, H4.05, N13.58.
Example 6:
synthesis of iron complex 5 containing m-carborane triazole ligand:
CuI (0.05mmol), 1, 3-dipropargylpyrocarbylborane (1.0mmol) and 4-bromoazidobenzene (1.3mmol) were dissolved in THF at room temperature, reacted at that temperature for 6 hours, and then FeCl was added2(1.0mmol) was added to the reaction system and reacted for an additional 6 hours. After the reaction, the reaction mixture was left to stand and filtered, and the solvent was dried under reduced pressure, and the obtained crude product was subjected to column chromatography (dichloromethane/ethyl acetate 4:1) to obtain brown iron complex 5 as an objective product (yield 81%).1H NMR(400MHz,CDCl325 ℃ C.: δ 8.39(s,2H),7.87(d, J ═ 7.2Hz,4H),7.79(d, J ═ 7.2Hz,4H),3.23(s,4H)20B10H25Cl2BrN6Fe: c36.16, H3.79, N12.65; experimental values: c36.20, H3.75, N12.69.
Example 7:
the iron complex 1 catalyzes ethylbenzene oxidation:
ethylbenzene (1.0mmol), iron complex 1(0.02mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 6 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained8H10O (91% yield).1H NMR(400MHz,CDCl3) δ 7.35 to 7.25(m,5H),4.86(q, J6.8 Hz,1H),2.36(brs,1H),1.48(d, J7.2 Hz, 3H). Theoretical values of elemental analysis C78.65, H8.25; experimental values: c78.69, H8.22.
Example 8:
the iron complex 1 catalyzes 2-methyl ethylbenzene oxidation:
2-methyl-ethylbenzene (1.0mmol), iron complex 1(0.02mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 8 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O (yield 93%).1H NMR(400MHz,CDCl3) δ is 7.52(dd, J is 7.2,1.5Hz,1H),7.27 to 7.22(m,1H),7.18(td, J is 7.2,1.5Hz,1H),7.15 to 7.12(m,1H),5.13(q, J is 6.4Hz,1H),2.35(d, J is 1.4Hz,3H),1.82(brs,1H),1.47(d, J is 6.4Hz, 3H). Theoretical values of elemental analysis C79.37, H8.88; experimental values: c79.41, H8.83.
Example 9:
the iron complex 1 catalyzes 4-methoxy ethylbenzene to be oxidized:
4-Methoxyethylbenzene (1.0mmol), iron complex 1(0.03mmol) and H2O2(1.2mmol) is dissolved in 2mL of methanol, the mixture reacts for 6 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O2(yield 95%).1H NMR(400MHz,CDCl3) δ is 7.27(t, J is 8.0Hz,2H),6.86(d, J is 8.0Hz,2H),4.82(q, J is 6.4Hz,1H),3.78(s,3H),2.08(brs,1H),1.45(d, J is 6.4Hz, 3H). Theoretical value of elemental analysis C71.03, H7.95; experimental values: c71.06, H7.99.
Example 10:
the iron complex 2 catalyzes 4-methyl ethylbenzene oxidation:
4-methyl-ethylbenzene (1.0mmol), iron complex 2(0.05mmol) and H2O2(1.3mmol) is dissolved in 2mL of methanol, the mixture reacts for 7 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O (yield 93%).1H NMR(400MHz,CDCl3) δ is 7.27(d, J is 8.0Hz,2H),7.16(d, J is 8.0Hz,2H),4.85(q, J is 6.4Hz,1H),2.34(s,3H),1.95(s,1H),1.47(d, J is 5.6Hz, 3H). Theoretical values of elemental analysis C79.37, H8.88; experimental values: c79.35 and H8.85.
Example 11:
the iron complex 2 catalyzes 4-nitroethylbenzene oxidation:
4-Nitroethylbenzene (1.0mmol), iron complex 2(0.03mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 8 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained8H9NO3(yield 96%). Theoretical values of elemental analysis C57.48, H5.43, N8.38; experimental values: c57.55, H5.45, N8.41.
Example 12:
the iron complex 3 catalyzes the oxidation of 3-methyl ethylbenzene:
3-methyl-ethylbenzene (1.0mmol), iron complex 3(0.05mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 6 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O (yield 95%).1H NMR(400MHz,CDCl3) δ is 7.31 to 7.09(m,4H),4.88(d, J is 6.4Hz,1H),2.40(s,3H),2.05(brs,1H),1.52(d, J is 6.4Hz, 3H). Theoretical values of elemental analysis C79.37, H8.88; experimental values: c79.31 and H8.83.
Example 13:
the iron complex 3 catalyzes 4-chloroethylene oxidation:
3-methyl-ethylbenzene (1.0mmol), iron complex 3(0.02mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 8 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained8H9ClO (96% yield).1H NMR(400MHz,CDCl3) δ is 7.29 to 7.25(m,4H),4.88 to 4.83(m,1H),1.97(brs,1H),1.45(d, J is 6.4Hz, 3H). Theoretical values of elemental analysis C61.35, H5.79; experimental values: c61.39, H5.82.
Example 14:
the iron complex 4 catalyzes n-propylbenzene to be oxidized:
n-propylbenzene (1.0mmol), iron complex 4(0.02mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 6 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O (yield 93%).1H NMR(400MHz,CDCl3) δ is 7.35 to 7.41(m,4H),7.27 to 7.34(m,1H),4.61(t, J is 6.4Hz,1H),2.01 to 2.14(m,1H),1.70 to 1.91(m,2H),0.94(t, J is 7.2Hz, 3H). Theoretical values of elemental analysis C79.37, H8.88; experimental values: c79.33, H8.93.
Example 15:
iron complex 4 catalyzes n-butylbenzene oxidation:
n-butylbenzene (1.0mmol), iron complex 4(0.05mmol) and H2O2(1.5mmol) was dissolved in 2mL of methanol and reacted at room temperature for 6H, directly carrying out silica gel column chromatography separation on the concentrated reaction solution after the reaction is finished, and drying until the quality is unchanged to obtain a corresponding product C10H14O (yield 96%).1H NMR(400MHz,CDCl3) δ is 7.38 to 7.24(m,5H),4.69 to 4.64(m,1H),2.02(brs,1H),1.79 to 1.64(m,2H),1.48 to 1.27(m,2H),0.94(t, J is 7.2Hz, 3H). Theoretical values of elemental analysis C79.96, H9.39; experimental values: c79.90, H9.37.
Example 16:
iron complex 5 catalyzes the oxidation of 2-ethylnaphthalene:
2-ethylnaphthalene (1.0mmol), iron complex 5(0.02mmol) and H2O2(1.3mmol) is dissolved in 2mL of methanol, the mixture reacts for 8 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained12H12O (yield 95%).1H NMR(400MHz,CDCl3) δ is 7.89 to 7.77(m,4H),7.55 to 7.45(m,3H),5.04(q, J is 6.4Hz,1H),2.33(brs,1H),1.58(d, J is 6.4Hz, 3H). Theoretical value of elemental analysis C83.69, H7.02; experimental values: c83.73, H6.98.
Example 17:
iron complex 5 catalyzes cumene oxidation:
cumene (1.0mmol), iron complex 5(0.03mmol) and H2O2(1.5mmol) is dissolved in 2mL of methanol, the mixture reacts for 8 hours at room temperature, after the reaction is finished, concentrated reaction liquid is directly subjected to silica gel column chromatography separation and dried until the mass is unchanged, and a corresponding product C is obtained9H12O (yield 92%).1H NMR(400MHz,CDCl3) δ is 7.52 to 7.48(m,2H),7.38 to 7.31(m,2H),7.26 to 7.22(m,1H),2.07 to 1.78(m,1H),1.58(s, 6H). Theoretical values of elemental analysis C79.37, H8.88; experimental values: c79.32, H8.90.
Example 18:
an iron complex containing a meta carborane triazole ligand, the iron complex having the formula:
wherein, R is H, and the- (G-B) -is a boron hydrogen bond.
The preparation method of the iron complex comprises the following steps:
1) adding n-BuLi n-hexane solution into m-carborane ether solution at-5 ℃, and then continuously stirring for 35 min; heating to room temperature, and continuing to react for 30 min;
2) adding 3-bromopropyne, reacting at room temperature for 4h, draining the solvent after the reaction is finished, and recrystallizing by n-hexane to obtain 1, 3-dipropargyl m-carborane;
3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst CuI in an organic solvent tetrahydrofuran, and then reacting for 3 hours at room temperature;
4) adding FeCl2And reacting at room temperature for 8h, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the iron complex. Wherein, the catalyst, 1, 3-dipropargyl meta-carborane, aryl azide and FeCl2Is 0.05:1.0:1.2: 1.
The iron complex is used for catalyzing and oxidizing aromatic hydrocarbon to synthesize aromatic alcohol. In the catalytic oxidation process, hydrogen peroxide is used as an oxidant.
Example 19:
an iron complex containing a meta carborane triazole ligand, the iron complex having the formula:
wherein, R is OMe, and the- (G-H) -is a boron hydrogen bond.
The preparation method of the iron complex comprises the following steps:
1) adding n-BuLi n-hexane solution into m-carborane ether solution at 5 ℃, and then continuously stirring for 25 min; heating to room temperature, and continuing to react for 60 min;
2) adding 3-bromopropyne, reacting at room temperature for 2h, draining the solvent after the reaction is finished, and recrystallizing by n-hexane to obtain 1, 3-dipropargyl m-carborane;
3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst CuI in an organic solvent tetrahydrofuran, and then reacting for 6 hours at room temperature;
4) adding FeCl2And reacting at room temperature for 5h, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the iron complex. Wherein, the catalyst, 1, 3-dipropargyl meta-carborane, aryl azide and FeCl2Is 0.05:1.0:1.5: 1.
The iron complex is used for catalyzing and oxidizing aromatic hydrocarbon to synthesize aromatic alcohol. In the catalytic oxidation process, hydrogen peroxide is used as an oxidant.
Example 20:
an iron complex containing a meta carborane triazole ligand, the iron complex having the formula:
wherein R is NO2And ". cndot.is a boron hydrogen bond.
The preparation method of the iron complex comprises the following steps:
1) adding n-BuLi n-hexane solution into m-carborane ether solution at 0 ℃, and then continuously stirring for 30 min; heating to room temperature, and continuing to react for 45 min;
2) adding 3-bromopropyne, reacting at room temperature for 3h, draining the solvent after the reaction is finished, and recrystallizing by n-hexane to obtain 1, 3-dipropargyl m-carborane;
3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst CuI in an organic solvent tetrahydrofuran, and then reacting for 4 hours at room temperature;
4) adding FeCl2And reacting for 7 hours at room temperature, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the iron complex. Wherein, the catalyst, 1, 3-dipropargyl meta-carborane, aryl azide and FeCl2Is 0.05:1.0:1.3: 1.
The iron complex is used for catalyzing and oxidizing aromatic hydrocarbon to synthesize aromatic alcohol. In the catalytic oxidation process, hydrogen peroxide is used as an oxidant.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. An iron complex containing a meta carborane triazole ligand, wherein the iron complex has the following structural formula:
wherein R is H, OMe, NO2One of Cl or Br, "·" is a boron hydrogen bond.
2. A process for the preparation of an iron complex containing a meta carborane triazole ligand as claimed in claim 1, comprising the steps of:
1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature;
2) adding 3-bromopropyne, reacting at room temperature for 2-4h, draining the solvent after the reaction is finished, and recrystallizing to obtain 1, 3-dipropargyl m-carborane;
3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst in an organic solvent, and reacting at room temperature for 3-6 h;
4) adding FeCl2Reacting for 5-8h at room temperature, and separating to obtain the iron complex.
3. The method for preparing the iron complex containing the m-carborane triazole ligand according to claim 2, wherein in the step 1), the n-BuLi solution is n-hexane solution of n-BuLi, and the m-carborane solution is ether solution of m-carborane.
4. The preparation method of the iron complex containing the m-carborane triazole ligand as claimed in claim 2, wherein the step 1) is specifically as follows:
1-1) dropwise adding the n-BuLi solution into the meta-carborane solution at the temperature of between-5 and 5 ℃, and then continuously stirring for 25 to 35 min;
1-2) heating to room temperature, and continuing to react for 30-60 min.
5. The preparation method of the iron complex containing the m-carborane triazole ligand as claimed in claim 2, wherein in the step 2), the solvent is drained after the reaction is finished, and the 1, 3-dipropargyl m-carborane is obtained by recrystallization through n-hexane.
6. The method for preparing an iron complex containing a m-carborane triazole ligand as claimed in claim 2, wherein in step 3), the catalyst is CuI, and the organic solvent is tetrahydrofuran.
7. The method for preparing the iron complex containing the m-carborane triazole ligand according to claim 2, wherein the separation process in the step 4) is as follows: after the reaction is finished, standing and filtering, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product.
8. The method for preparing the iron complex containing the m-carborane triazole ligand according to claim 2, wherein the catalyst, the 1, 3-dipropargyl m-carborane, the aryl azide and the FeCl2The molar ratio of (1) to (1.2-1.5) is 0.05:1.0 to 1.
9. Use of an iron complex comprising a meta carborane triazole ligand according to claim 1, wherein said iron complex is used to catalyze the oxidation of aromatic hydrocarbons to aromatic alcohols.
10. The application of the iron complex containing the m-carborane triazole ligand as claimed in claim 9, wherein hydrogen peroxide is used as an oxidant in the catalytic oxidation process; the aromatic hydrocarbon comprises one or more of ethylbenzene, 2-methyl ethylbenzene, 3-methyl ethylbenzene, 4-methoxy ethylbenzene, 4-chloro ethylbenzene, 4-nitro ethylbenzene, n-propylbenzene, n-butylbenzene, 2-ethyl naphthalene or isopropylbenzene.
CN201910928582.2A 2019-09-28 2019-09-28 Iron complex containing m-carborane triazole ligand and preparation and application thereof Active CN110627841B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910928582.2A CN110627841B (en) 2019-09-28 2019-09-28 Iron complex containing m-carborane triazole ligand and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910928582.2A CN110627841B (en) 2019-09-28 2019-09-28 Iron complex containing m-carborane triazole ligand and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN110627841A true CN110627841A (en) 2019-12-31
CN110627841B CN110627841B (en) 2021-05-11

Family

ID=68973505

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910928582.2A Active CN110627841B (en) 2019-09-28 2019-09-28 Iron complex containing m-carborane triazole ligand and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN110627841B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111454296A (en) * 2020-04-07 2020-07-28 上海应用技术大学 Palladium complex containing m-carborane triazole ligand and preparation method and application thereof
CN111454298A (en) * 2020-04-07 2020-07-28 上海应用技术大学 Nickel complex containing m-carborane triazole ligand and preparation method and application thereof
CN111732613A (en) * 2020-06-08 2020-10-02 上海应用技术大学 Ferric iron complex containing meta-carborane ligand and preparation method and application thereof
CN114716484A (en) * 2022-03-10 2022-07-08 上海应用技术大学 Ferric iron complex containing m-carborane methylpyridine structure and preparation and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432640A (en) * 2011-10-09 2012-05-02 复旦大学 Half-sandwiched iridium (Ir) and rhodium (Rh) compound having carborane-amidine-containing structure, and preparation method and application of half-sandwiched Ir and Rh compound
WO2013082150A1 (en) * 2011-11-30 2013-06-06 The Curators Of The University Of Missouri Small molecule inhibitors of nicotinamide phosphoribosyltransferase (nampt)
CN106008584A (en) * 2016-06-01 2016-10-12 哈尔滨工业大学无锡新材料研究院 Method for controlling carborane derivative structure by click reaction
CN108620130A (en) * 2018-07-10 2018-10-09 上海应用技术大学 The o-C of carborane containing ortho position2B10H10The trivalent complex of iridium of structure, preparation method and applications
CN110117299A (en) * 2019-05-30 2019-08-13 上海应用技术大学 The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432640A (en) * 2011-10-09 2012-05-02 复旦大学 Half-sandwiched iridium (Ir) and rhodium (Rh) compound having carborane-amidine-containing structure, and preparation method and application of half-sandwiched Ir and Rh compound
WO2013082150A1 (en) * 2011-11-30 2013-06-06 The Curators Of The University Of Missouri Small molecule inhibitors of nicotinamide phosphoribosyltransferase (nampt)
CN106008584A (en) * 2016-06-01 2016-10-12 哈尔滨工业大学无锡新材料研究院 Method for controlling carborane derivative structure by click reaction
CN108620130A (en) * 2018-07-10 2018-10-09 上海应用技术大学 The o-C of carborane containing ortho position2B10H10The trivalent complex of iridium of structure, preparation method and applications
CN110117299A (en) * 2019-05-30 2019-08-13 上海应用技术大学 The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111454296A (en) * 2020-04-07 2020-07-28 上海应用技术大学 Palladium complex containing m-carborane triazole ligand and preparation method and application thereof
CN111454298A (en) * 2020-04-07 2020-07-28 上海应用技术大学 Nickel complex containing m-carborane triazole ligand and preparation method and application thereof
CN111454296B (en) * 2020-04-07 2023-04-28 上海应用技术大学 Palladium complex containing meta-carborane triazole ligand and preparation method and application thereof
CN111732613A (en) * 2020-06-08 2020-10-02 上海应用技术大学 Ferric iron complex containing meta-carborane ligand and preparation method and application thereof
CN114716484A (en) * 2022-03-10 2022-07-08 上海应用技术大学 Ferric iron complex containing m-carborane methylpyridine structure and preparation and application thereof

Also Published As

Publication number Publication date
CN110627841B (en) 2021-05-11

Similar Documents

Publication Publication Date Title
CN110627841B (en) Iron complex containing m-carborane triazole ligand and preparation and application thereof
CN110117299B (en) Rhodium complex containing ortho-carbon boron alkyl benzimidazole structure and preparation and application thereof
CN112778533B (en) Porphyrin-based porous organic polymer, preparation method thereof and synthesis method of cyclic carbonate
CN109575087B (en) Binuclear half-sandwich iridium complex containing diimine ligand, preparation method and application thereof
CN111961087B (en) Semi-sandwich ruthenium complex containing ortho-position carborane-based benzothiazole, and preparation and application thereof
CN112645836B (en) Heterogeneous catalyst Cu @ COF-Me-M and preparation method and application thereof
CN112375105B (en) Application of N, N-coordinated divalent nickel complex containing meta-carborane ligand
CN111454296A (en) Palladium complex containing m-carborane triazole ligand and preparation method and application thereof
CN110204580B (en) Divalent nickel imine complex containing nickel-nitrogen double bond structure and preparation and application thereof
CN113105301B (en) Method for preparing conjugated diyne compound by using copper complex
CN112871218B (en) Neutral nickel complex containing ortho-carborane-based benzothiazole, and preparation and application thereof
CN112661667B (en) Preparation method of trifluoroacetamidine
CN111454298A (en) Nickel complex containing m-carborane triazole ligand and preparation method and application thereof
CN112538096B (en) Application of half-sandwich rhodium complex containing ortho-carboranyl benzoxazole structure
CN112961176B (en) Preparation method of boron-dioxygen ring neutral radical compound
CN114853608A (en) Synthetic method of [60] fullerene hydrogen derivative catalyzed by N-heterocyclic carbene
CN107935803B (en) Synthetic method of 1, 2-diketone compound
CN114315594B (en) Method for catalytically synthesizing chiral amine compound by using rhodium complex
CN111732613A (en) Ferric iron complex containing meta-carborane ligand and preparation method and application thereof
CN111675736A (en) Rhodium complex containing ortho-carborane Schiff base ligand and preparation method and application thereof
CN113121402B (en) Method for preparing 3-alkynyl indole compound by using gold complex
CN114213383B (en) Method for catalytically synthesizing isocoumarin compounds by using ruthenium complex
CN110981702B (en) Efficient synthesis method of 2, 3-dibromophenol or derivatives thereof
CN112645984B (en) Half-sandwich ruthenium complex containing phenyl benzoxazole structure and preparation method and application thereof
CN113185435B (en) Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant